Iranian Journal of Hydrogen & Fuel Cell 1(2014) 1-10

Iranian Journal of Hydrogen & Fuel Cell

IJHFC
Journal homepage://ijhfc.irost.ir
Determination of thermodynamic parameters of hydrogen permeation
of palladium membrane for considering the effect of stainless steel
support
Mohammadamir Saadatinasab
1
, Hussein Gharibi
*1,2
, Alireza Zolfaghari
3
1
Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
2
Department of Material Science & Engineering, 122 S Campus Drive, University of Utah, Salt Lake City, Utah 84112, USA
3
Department of Physical Chemistry, Chemistry and Chemical Research Center of Iran, Tehran, Iran
Article Information

Article History:
Received:
7 July 2013
Received in revised form:
14 December 2013
Accepted:
26 January 2014
Keywords
Palladium composite membrane
Enthalpy of hydrogen dissolution
Porous stainless steel support
Abstract
A palladium composite membrane was prepared by electroless plating on
through this composite membrane was measured in the temperature range
of 574-674 K and the pressure difference of two sides of membrane up to
tion behavior of hydrogen through Pd/ox-PSS membrane for calculating the
contribution of each layer in resistance against the hydrogen transport. The
amount of enthalpy of hydrogen dissolution of palladium membrane is -9.4
kJ/mol.
Considering a complete detailed model, this value was used for discussing the
effect of interaction of metal- support on hydrogen exiting from the palladium
layer at the downstream side. Several composite membranes which differ in
metal-support interaction, plays an effective role in exiting activation energy.
In Pd/ox-PSS composite membrane, the metal-support interaction decreases
hydrogen exiting rate from Pd membranes downstream side.
*Corresponding author. E-mail: h.gharibi@gmail.com
Tel: +98 - (21) 8288 - 4401 (Tarbiat Modares University, Tehran, Iran)
Fax: +98 - (21) 8288 - 4401 (Tarbiat Modares University, Tehran, Iran)
1. Introduction
Need to clean and healthful environment forces
the world to the pure hydrogen production and fuel
cell application. However, almost all of the ener-
gy carriers are fossil fuels and hydrocarbon com-
pounds. Production of clean and green hydrogen
fuel from these energy carriers is performed in rel-
atively high temperature through steam reforming
reaction. For hydrogen separation purposes, pal-
ladium based membranes have been studied in
many investigations owing to their suitable prop-
erties at high temperature, high permeability, se-
lectivity and durability.
In order to construct the membrane, various sup-
anodic alumina [4], porous Hastelloy [5], and dif-
ferent diffusion barriers (e.g. Cr
2
O
3 2
O
3

[7], ZrO
2
[8], TiO
2
[9], SiO
2
[10], CeO
2
[11]) have
been used. Also, various palladium-based alloys
have been used. Also, various palladium-based
alloys have been used as membrane such as Pd-
Cu [12], Pd-Ag [13], Pd-Au and Pd-Au-Pt [14],
Pd-Cu-Ni [15], Pd-Cu-Au [16], Pd-Cu-Ag [17],
and other binary and ternary alloys [18]. In addi-
tion, membranes with different micro-structures
[19,20], and geometries [21,22] have been used
to evaluate the performance of them. However,
the contribution of support in the permeation
process has not been concern, particularly in ex-
perimental procedure.
Although there are few reports. Huang et. al., by
2
O
3
composite membranes,
reported hydrogen permeation activation energy,
molar enthalpy and entropy of hydrogen dissolu-
tion in palladium layer [23].Zhang et. al., com-
pare their data with a model and they investigate
the effects of different diffusion barriers on the
activation energy of hydrogen permeation [24].
In this study, we prepared a Pd/ox-PSS mem-
brane and studied its permeation behavior. In the
next section, the background theory of permea-
tion through composite palladium membrane is
explained. Then, the experimental procedure is
stated. Finally, the contributions of Pd layer and
support for hydrogen permeance are calculated.
Furthermore, palladium layers permeability, hy-
drogen permeation activation energy, molar en-
thalpy and entropy of hydrogen dissolution in Pd
layer are investigated.
2. Theory
A composite palladium membrane consists of
a porous support and a thin layer of palladium.
Although in many researches, the support effect
is disregarded but it affects on the characteristics
of permeation through the composite palladium
membrane. To differentiate the contributions of
porous support and palladium layer in the perme-
ation resistance, we used the resistance model.
This model was developed by Henis and Tripodi
for gas permeation in a composite membrane
[25]. The permeation resistance of a layer is de-
to this model, the permeation behaviour of gas
through a composite membrane is analogous to
resistors.
ure 1 shows the schematic of composite mem-
brane resistance model for a dense palladium
composite membrane. The transport resistances
Iranian Journal of Hydrogen & Fuel Cell 1(2014) 1-10
2
in the support and palladium layer have been
symbolized by R
s
and R
Pd
, respectively.
The total resistance of the composite membrane
R
tot
, is the sum of resistances in the palladium
layer and the support layer:
(1)
Where
F
tot
is the composite membrane permeance, and
P
h
, P
i
and P
l
are feed side pressure (high pres-
sure side), pressure (high pressure side), pressure
in the palladium-support interface and permeate
side pressure (low pressure side), respectively.
The permeance through porous support
In pressure-driven gas permeation process
through a bare porous support, the transport
mechanism mainly follows Knudsen diffusion
through a bare porous disk vs. trans-membrane
average pressure is correlated by a straight line:
(2)
(3)
The slope and intercept of the latter equation rep-
and Knud-
sen diffusion, respectively. F
k,s
and F
v,s
(4)
(5)
Figure 1. Schematic representation of H
2

permeation through Pd composite membrane.
1
tot s Pd
tot
R R R
F
,
i l
s
P P
R
J
h i
Pd
P P
R
J
( )
h l
J F P P
, ,
.
k s v s av
F F F P
,
4 2 1
3
k
k s
r
F
L R MT
2
,
1
8
k
v s
r
F
RL T
Iranian Journal of Hydrogen & Fuel Cell 1(2014) 1-10
3
F
k,s
and F
v,s
for a given porous media, and the second items
are functions of gas molecular mass and temper-
ature.
The permeation through Palladium layer

by the solution-diffusion mechanism can be ex-
pressed as follows:
(6)
If adsorption and desorption of hydrogen mole-
cules (surface process) are done quickly, then the
diffusion of hydrogen in the bulk palladium layer
is described by:
(7)
Where
The temperature dependence of permeability F
pl

D, can be expressed by
an exponential form as the below equations:
(8)

(9)
The molar values for the enthalpy of hydrogen
dissolution,
H H
and the entropy of hydrogen dis-
solution in palladium layer H S , could be calcu-
lated by:
(10)
The contribution of palladium layer in permea-
tion resistance
In a composite membrane, to obtain hydrogen
permeance through Pd layer only and the con-
tribution of this layer in the transport resistance,
hydrogen pressure at palladium-support interface
P
i
, should be calculated by the resistances in se-
ries model as below:
n n
h l
J F P P
0.5 0.5
h l
pl
P P
J F
L
b
pl
s
N
F DS D
K
,0
exp
a
pl pl
E
F F
RT
0
exp
d
E
D D
RT
exp
H H
s
H S
K
RT R
(11)
This equation easily can be derived by consider-
ing the resistance model and solving Eq. (3) for
calculating pressure at the interface.
3. Experimental procedure
3.1. Membrane preparation
PSS 316L disk with nominal particle retention
chased from Mott metallurgical corporation.
According to the manufacturer, the disk has a
porosity of roughly 2023%. Such a plate made
by metal powders has been widely used as the
substrate to provide mechanical strength for pal-
ladium membrane. The PSS support was cleaned
in an ultrasonic bath with a mixture of an alka-
line sodium solution and an organic detergent at
333K for 30 min. The cleaning procedure was
followed by rinsing in deionised water and iso-
propanol, respectively.
port at 393K for 3h.
Then it was oxidized in the stagnant air at 1173K
for 12h to form an oxide intermetallic diffusion
barrier at the intermediate of the support and the
hydrogen selective Pd layer. Before electroless
plating, the disk was sensitized and activated ac-
cording to a conventional SnCl
2
/PdCl
2
method
[26]. Pd membrane was prepared using electro-
less plating over the ox-PSS disk support. The
chemicals and conditions required for electroless
The volume/area ratio between the plating solu-
tion and the plated area was kept about 3cm
3
/cm
2
.
3.2. Membrane permeation testing
A conventional homemade disk type setup was
used to measure the permeation of gas through
the prepared membrane. The composite mem-
brane was assembled in the compact testing cell,
and the perimeter of that, was sealed fully with
a high temperature resistant silver paste. The
valid membrane diameter for the permeation test was
measured by introducing into the palladium mem-
brane disk. Measurement of hydrogen permeation
1 2
2
, , , 2
, , , ,
2
2
k s k s k s
i l l
v s v s v s v s
F F F J
P P P
F F F F
Iranian Journal of Hydrogen & Fuel Cell 1(2014) 1-10
4
Table 1. Palladium plating bath composition and
conditions
sures. Before testing, the membrane was heated
in nitrogen atmosphere up to 674K at 1K/min.
Then the nitrogen introducing gas substituted
urements at 674K and different pressures up to
90kPa, the temperature was lowered, and the ex-
periment was repeated at the next point. At each
ment continues some time to ensure of reach-
ing to stability and equilibrium conditions. The
subsequent calculations. The pressure at the per-
meate side was always ambient (87.7kPa) with-
out purging gas in any of the experiments. The
of its pressure at the membrane feed side by soap
3.3. Characterization

Microstructural images of PSS and the mem-
brane were taken by scanning electron micro-
scope (SEM TESCAN/VEGA xmu). Pd layer
thickness was measured by SEM, too.
4. Results and discussion
In the composite palladium membrane, the plat-
ing substrate should be neither too coarse to pre-
2a and 2b show SEM micrographs of the cleaned
PSS surface before and after oxidation, respec-
tively. Although the surface of PSS is smooth,
the morphology of the ox-PSS, presented in Fig-
ure 2b, shows homogenous nanoscale coarsen
surface, which increases the metal-support inter-
action surface area. Figure 3 shows the morphol-
ogy of the prepared membrane.As can be seen,
the membrane has a compacted coating which
According to the permeation test, the composite
palladium membrane showed zero nitrogen per-
meation lux at room temperature and the pressure
difference of 1 bar.
Figure 2. SEM micrographs of: a) the PSS disk surface
before and b) after surface oxidation.
It means that at this condition, nitrogen permea-
-5
mol/m
2
.s, based on
the permeation test equipment limit. SEM mi-
crograph of the membranes cross-section shows
In order to calculate the amounts of viscose
Figure 3. SEM micrograph of electrolessly plated
palladium membrane.
and Knudsen constants for the ox-PSS support,
we placed it in the permeation test cell and fed
with hydrogen. Figure 4 shows the hydrogen
Iranian Journal of Hydrogen & Fuel Cell 1(2014) 1-10 5
permeances at various trans-membrane average
pressures at room-temperature for ox-PSS sup-
port. The regressed values for the constants of
F
k,s
(mol/ m
2
.s.Pa) and F
v,s
(mol/ m
2
.s.Pa
2
) at
room temperature are 1.3510
-5
and 1.6210
-10
,
respectively. By measuring F
k,s
and F
v,s
in one
temperature, their values can be calculated for
(4) & (5)].
Figure 4. Hydrogen permeance of the support as a
function of average pressure.
By using Eq. (11) the pressure at the interface
was obtained. Then the permeance and resistance
of each layer was calculated. Figure 5 shows the
percentage of the palladium layer permeation
resistance to composite membrane permeation
resistance at different temperatures, where the
feed side pressure of the membrane is adopted
as the abscissa. It is shown that the support has
averagely a contribution of 5% in hydrogen
permeation resistance that is large enough
to consider it in calculating thermodynamic
properties of hydrogen permeation through
palladium layer.
Figure 5. The ratio of R
Pd
/R
tot
(%) vs. feed side pressure
at different temperatures:

674K, 624K,

574K.
It can be seen that by rising of temperature, the
palladium layers resistance decreased. It is due
to the enhancement of palladium bulk permeance
induced by temperature rise. In addition, more
pressure in the feed side, leads to more palladium
layer contribution in composite membrane per-
meation resistance.
Considering the Pd layer separately, the depend-
ence, is shown in Figure 6.
the palladium layer at different temperatures: 674K,
624K,

574K.
vs. pressure difference obtains with pressure ex-
ponent of 0.5. This means that the determining
step of permeation rate is bulk diffusion process.
Figure 7 shows the effect of temperature on the
hydrogen permeance through the Pd layer. From
the Arrhenius plot, the activation energy of hy-
drogen permeation through Pd layer in this mem-
brane was evaluated to be 12.83kJ/mol.
Generally, hydrogen permeation through dense
palladium layer involves several steps in series.
These are in order from the feed side to the per-
meate side as:(1) molecular hydrogen transport
from the bulk gas to the gas layer near the surface
(2) dissociative adsorption (chemisorption) (3)
atomic hydrogen absorption into the bulk metal
(surface to bulk transition) (4) diffusion of the
atomic hydrogen through the membrane via the
lattice structure (5) transition of atomic (bulk to
surface transition) (6) re-associative desorption
of the hydrogen atoms into molecular hydrogen
(7) movement of the resulting hydrogen mol-
ecules away from the downstream surface of the
membrane [22]. At equilibrium, the adsorption
and desorption rates (steps 2 and 6), are equal, as
Iranian Journal of Hydrogen & Fuel Cell 1(2014) 1-10 6
are the transition rates between the surface and
the bulk metal, i.e. surface-to-bulk metal transi-
tion (step 3) and bulk metal-to-surface transition
(step 5). Each of these steps is characterized by a
rate equation. Equating and combining these ex-
pressions as formulated by Ward and Dao, and
using the ideal gas law, leads to the following re-
lationship [27]:
(12)
E
A
, E
B
and E
d
are activation energies for H at-
oms surface-to-bulk metal transition, activation
energy for H atoms bulk metal-to-surface tran-
sition, and activation energy for hydrogen des-
orption, respectively. This equation shows that
molar enthalpy of dissolution is proportional to
E
A
-(E
B
+E
d
). It means that less activated H atoms
transiting from upstream surface to bulk of the
palladium layer (less E
A
) and/or more activated
hydrogen exiting from the downstream surface
of the palladium layer (more E
B
and E
d
) make the
molar enthalpy of dissolution to be more nega-
tive and vice versa.
Enthalpy of hydrogen dissolution in palladium
layer can be calculated considering Eqs. (7)-(10).
Data for hydrogen diffusion in palladium layer
have been reported by a number of researchers
[28-30]. There is some variation, but most values
are reasonably consistent. We have chosen to use
parameters based on thosereported by Holleck
[28]. They have been determined in the tempera-
ture range of 533-913K for a thick palladium foil
that hydrogen diffuses through palladium bulk.
In this electroless plated palladium layer, as can
be seen in Figure 3, the grain sizes appear to be
diffusion through the grain boundaries is not ex-
data of D
0
=2.9410
-7
m
2
/s and E
d
=22.2kJ/mol ac-
hydrogen at different temperatures were calculat-
ed. Then, the solubility constants were evaluated
by Eq.(7). By calculating the Sieverts constants
at different temperatures (K
s
), thermodynamic
parameters have been obtained [Eq. (10)]. Based
on this calculation, the enthalpy and entropy of
hydrogen dissolution in the palladium layer ob-
0.5
0.25 2
0.5
0 0
0.5
0 0
2 1
exp
exp exp
s A B d
H H
k N MRT F E E E
S G RT
S H
R RT
tained as -9.4kJ/mol and -55.3J/mol.K, respec-
tively. Few researchers report the molar enthalpy
of hydrogen dissolution in palladium membrane
[23, 28]. We used enthalpy of hydrogen dissolu-
tion in palladium layer of different membranes
in order to compare their behaviour in hydrogen
permeation steps. These values have been com-
pared with each other in Table 2.
Table 2. A comparison of interdiffusion parameters of
hydrogen through the Pd layer.

a
prepared by electroless plating method
b
These amounts extracted from reference data.
Note that all of them have been measured by
considering only palladium layer contribution in
permeance using the same diffusion parameters
as Holleck. The value of H H reported by Hol-
leck [28] is -8.4kJ/mol. Comparison between our
membrane and the Pd/Al
2
O
3
composite mem-
brane prepared by Huang, shows good accord-
ance with each other in the value of H H but is
more negative than the value reported by Hol-
leck. Since Holleck used self supported mem-
brane, this difference should be attributed to
metal-support interaction. This is the main dif-
ference.of Hollecks membrane with fabricated
membrane in our lab and Huangs membrane
[23]. In contrast to Pd/ox-PSS and Pd/Al
2
O
3
, the
value of H H in palladium layer of Pd/YSZ-Al
2
O
3

composite membrane prepared by Zhang et. al. is
similar to this value of Hollecks self supported
palladium layer [24].
Given that all four membranes are made of pure
palladium and considering the main difference
between these palladium membranes i.e. support
material and based on the direct proportion be-
tween H H and E
A
-(E
B
+E
d
), more negative value
of H H implies to higher E
B
+E
d
. It means acti-
vated hydrogen exiting from downstream side of
palladium layer, might be related to metal-sup-
port interaction in these membranes. It is known
that the oxides are reduced to metallic state under
H
2
atmosphere. After that, supports metal ele-
ments and palladium could migrate and diffuse to
opposite layer. More chemical activity of support
Iranian Journal of Hydrogen & Fuel Cell 1(2014) 1-10 7
causes to more diffusion and alloying with pal-
ladium layer. The investigation and comparison
between Fe
2
O
3
, Al
2
O
3
and YSZ, indicates high
chemical activity of Fe
2
O
3
and Al
2
O
3
and inert-
ness of YSZ [24,32,33]. Using cross sectional
SEM and EDS of palladium supported mem-
branes, Akis and Okazaki, showed that in com-
posite palladium membranes Fe and Al are al-
loyed with palladium while no alloying occurs
between Palladium and Yttrium or Zirconium of
YSZ [32,33]. The formation of Pd-Fe and Pd-Al
alloys lower the hydrogen solubility and diffu-
sivity and increase the activation energy for hy-
drogen exiting [34,35]. In the case of Pd/YSZ-
Al
2
O
3
composite membrane, since Yttrium and
Zirconium is more inert and stable as the support,
no alloy layer might form in the palladium-sup-
port interface of Pd/YSZ-Al
2
O
3
membrane [32].
In fact, in the Holecks and Zhangs membranes,
H exiting is less activated step and the value of
obtains more positive.
This analysis shows that the support has an im-
portant role in permeation characteristics. In ad-
dition, it is reasonable to say that the molar en-
thalpy of hydrogen dissolution can be used to
compare chemical activity of support surface in
different composite membranes.
5. Conclusion
A palladium membrane was prepared on ox-
PSS support by electroless plating method. It
was shown that the support layer has averagely
a contribution of 5% in hydrogen permeation re-
sistance of the composited membrane. The per-
meation data of palladium layer was evaluated
and the activation energy of hydrogen permea-
tion and the molar enthalpy of hydrogen disso-
lution were calculated. The molar enthalpy of
hydrogen dissolution in palladium layer depos-
ited on ox-PSS obtained as -9.4kJ/mol which
is similar to the value of H H palladium layer
deposited on Al
2
O
3
and more negative than this
value of self supported palladium layer and the
palladium layer deposited on YSZ. Using a com-
plete model, it was deduced that molar enthalpy
of hydrogen dissolution is directly proportional
with E
A
-(E
d
+E
B
). By comparing several compos-
ite membranes which differ in support material,
tion, plays an effective role in exiting activation
energy. In Pd/ox-PSS composite membrane, the
metal-support interaction decreases hydrogen ex-
iting rate from Pd membranes downstream side.
Nomenclature
in Pd (m
2
/s)
D
0
Pre-exponential factor for
D(m
2
/s)
S Solubility constant
F Permeance (mol/m
2
.s.Pa)
F
p
l Permeability (mol.m/m
2
.s.Pa
-n
)
F
pl0
Pre-exponential factor for F
pl

(mol.m/m
2
.s.Pa
-n
)
E
A
Activation energy for H atoms
surface-to-bulk metal transition
(kJ/mol H)
E
B
Activation energy for H atoms
bulk metal-to-surface transition
(kJ/mol H)
E
d
Hydrogen desorption activation
energy (kJ/mol H)
F( ) , G( ) Functions of coverage factor

H H
Molar enthalpy of hydrogen dis
(kJ/mol H)

H S
Molar entropy of hydrogen
(kJ/mol K H)
J Flux through composite membrane
(mol/m
2
s)
K
s
Sievert's law constant
N
b
Bulk metal Pd atom concentration
(mol Pd/m
3
)
S
0
(at zero
coverage)
T Absolute temperature (K)
r Pore radius (m)
M Molecular mass (kg/mol)
Iranian Journal of Hydrogen & Fuel Cell 1(2014) 1-10
8
R Universal gas constant
(8.314 J/molK)
L Membrane thickness (m)
k
0
Desorption rate constant pre-
exponential factor
Greek letters
(Pa s)
(atomic H/Pd
ratio on surface)
(cm
3
/mol H s)
(cm
3
/mol H s)
Subscripts/Superscripts
av average
s support
p pinhole
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